Copper complex compounds of trisazo dyestuffs



United States Patent COPPER COMPLEX COIVIPOUNDS OF TRISAZO DYESTUFFS Fritz Suckfiill, Leverkusen-Wiesdorf, and Paul Zervas, Koln-Dellbruck, Germany, assignors torFarbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany complex compounds of trisazo dyestufis of the following general formula:

SOJH

In this formula X stands for hydrogen of methyl, alk stands for methyl or ethyl, and aeyl stands for the radical of a monocarboxylic acid.

The new trisazo dyestuffs and their copper complex compounds are obtainable by coupling the diazotized monoazo dyestufi's of the formula:

I SOaH SOaH with a 1-amino-2-alkoxynaphthalene-sulfonic acid, diazotizing the aminodisazo dyestutf thus obtained, coupling it with a 1-acylamino-8-hydroxy-naphthalene-sulfonic acid, and finally treating the trisazo dyestuff, thus pre- "ice Example 1 52.1 parts of the di-sodium salt of the aminoazo dyestuff of the following formula:

SOaH SiOaH are. dissolved in 700 parts of warm water and, after adding a solution of 8 parts of sodium nitrite, indirectly diazotized with 50 parts of hydrochloric acid (19 B.) for 3 hours at 3 to 5 C. The isolated diazo compound, after adding 300 parts of ice-water, is added to a solution of 28.9 parts of the sodium salt of l-amino-Z-ethoxynaphthalene-G-sulfonic acid at 10 to 15 C. After about 12 hours the coupling is completed, whereupon the aminodisazo compound is dissolved with 13.3 parts of caustic soda solution (specific gravity 1.33) and indirectly diazotized with a solution of 8 parts of sodium nitrite and 135 parts of hydrochloric acid (19 B.) for OH NH.acy1

SOaH

3 hours at 28 to 30 C. The diazodisazo compound is combined with 28.1 parts of l-aeetylamino-S-hydroxynaphthalene-4-sulfonic acid in the presence of 45 parts of sodium bicarbonate and 300 parts of pyridine at 0 C. After the coupling is completed, the trisazo dyestufi obtained is salted out at 60 C., isolated and redissolved. The dyestufi paste obtained is dissolved in 4000 parts of water and converted into the complex copper compound by 2 hours heating with 24 parts of crystallized copper sulfate in the presence of 10 parts of 50% acetic acid and l5'parts of crystallized sodium acetate to 98 to 100 C., the copper complex being separated by salting out of the weakly alkaline solution. It is the copper complex compound of the trisazo dyestuif corresponding as free acid to the formula:

403E S OaH and dyes cotton fast clear olive-green shades.

Example 2 52.1 parts of the di-sodium salt of the aminoazo dyestutf of the formula:

sloaH 8103B are diazotized according to Example 1. The diazoazo compound is coupled with 1-amino-Z-ethoxynaphthalene- 6-sulfonie acid, the aminodisazo compound is further diazotized, and the-diazodisazo compound is coupled with 29.5" parts of 'l-propionylamino-8-hydroxynaphthalene- 4-sulfonic acid and converted into the complex copper compound. The copper-containing trisazo dyestutf obtained dyes cotton clear olive-green shades. It is the naphthalene-4-sulfonic acid. The trisazo dyestuti'concopper complex of the dyestufi corresponding as free acid verted into the complex copper compound, dyes cotton to the formula: V olive-green clear shades. The new dyestuff is the copper OH NH.G 0.02115.

50311 I SO3H When the 1-propionylamino-8-hydroxynaphthalene-4- complex compound of the trisazo dyestutf corresponding sulfonic acid is replaced by equirnolecular quantities of as free acid to the formula:

$134 OH OH NELCOCH:

. a I I sozn ' S 0 3H 0 3H SOzE 1-benzoylamjno-8-hydroxynaphthalene-4-sulfonic acid, a We claim: similar dyestuff is obtained. 1. Copper complex compounds of trisazo dyestuffs corresponding as free acids to the general formula:

SOHH

Example 3 53.5 parts of the di-sodium salt of the aminoazo dyewherein X stands for one of the group consisting of hystuff of the formula: V V drogen' and methyl, alk stands for one of the group con- CH3 303E sisting of methyl and ethyl, and acyl stands for the radical of a monocarboxylie acid.

C1H5ON=N 2. The copper complex compound of the trisazo dye- V stufi corresponding as free acid to the formula:

AOEH V 40 80311 BOaH SOsH SOaH are indirectly diazotized, coupled with 26.7 parts'of 1- 3. The copper complex compound of the trisazo dye- .amino-2-ethoxynaphthalene-6-sulfonic acid, further distuff corresponding as free acid to the formula:

OH OH NH.CO.G2]E[5 CQH5OQ-N=NQ N= N=N soini $0311 7 V 03H A0311 azotized, and the diazodisazo compound thus obtained 4. The copper complex compound of the trisazo dyeis coupled with 28.1 parts of 1-acetylamino-8-hydroxystuff corresponding as free acid to the formula:

' CH; 0H NH.COCH3 O H l i 01H OaH I References Cited in the file of this patent UNITED STATES PATENTS 1,927,103 Taube et a1 Sept. 19, 1933 2,216,258 Weinand et a1. Oct. l, 1940 2,282,331 Krebser et al. May 12, 1942 

1. COPPER COMPLEX COMPOUNDS OF TRISAZO DYESTUFFS CORRESPONDING AS FREE ACIDS TO THE GENERAL FORMULA: 